Core-shell fluorescent nanoparticles

- Bridgestone Corporation

A fluorescent nanoparticle includes a core comprising an alkenylbenzene; an intermediate layer, an outer shell layer, and a fluorescent portion. The fluorescent portion includes a structure represented by the following formula: wherein L is a direct bond or a linker group, and F is any fluorescent moiety. The fluorescent portion is located in at least one of the following locations: the core, the intermediate layer, or the shell layer of the nanoparticle. Methods for making the fluorescent nanoparticle are also described.

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Description
FIELD

The technology disclosed herein is generally related to fluorescent nanoparticles. More particularly, it relates to a fluorescent nanoparticle comprising a core, an intermediate layer, and a shell. This disclosure also provides a method of making the fluorescent nanoparticles.

BACKGROUND

Fluorescent microparticles may be prepared by several practical methods from a variety of polymerizable monomers, including styrenes, dienes, acrylates and unsaturated chlorides, esters, acetates, amides and alcohols. For example, U.S. Pat. No. 4,326,008 to Rembaum discloses fluorescent microspheres obtained by copolymerizing an acrylic monomer containing a covalent bonding group such as hydroxyl, amine, or carboxyl with a fluorescent co-monomer such as dansyl allyl amine. U.S. Pat. No. 5,194,300 to Cheung and U.S. Pat. No. 4,774,189 to Schwartz disclose fluorescent microspheres that are coated by covalently attaching to their surface one or more fluorescent dyes. U.S. Pat. No. 5,073,498 to Schwartz and U.S. Pat. 4,717,655 to Fulwyler disclose fluorescent dyes added during particle polymerization process. In Uniform Latex Particles; Seragen Diagnostics Inc. 1984, p. 40, L. B. Bangs describes a method of internally embedding or diffusing a dye after particles have been already polymerized. U.S. Pat. No. 5,723,218 to Haugland et al. discloses diffusely dyeing microparticles with one or more dipyrrometheneboron difluoride dyes.

Fluorescent particles to which biological molecules have been attached have been used for immunoassays, as described, for example, in U.S. Pat. No. 4,808,524 to Snyder et al.; as labels for cell surface antigens, as described, for example, in Jett, Keller, Martin, Nguyen, & Saunders, Ultrasensitive Molecular-Level Flow Cytometry, in FLOW CYTOMETRY AND SORTING, p. 381, 2nd ed., Wiley-Liss Inc., N.Y. 1990; and as tracers to study cellular metabolic processes, as described, for example, in Hook & Odeyale, Confocal Scanning Fluorescence Microscopy: A New Method for Phagocytosis Research, J. LEUKOCYTE BIOL. 45: 277 (1989).

Particles based on micelle formation are also known, for example, U.S. Pat. Nos. 6,437,050, 6,689,469, 6,956,084, 7,112,369, which are hereby incorporated by reference in their entirety. These patents disclose the method of making styrene-core and butadiene-shell micelle particles. Related publications include “Dendrimers and Dendrons, Concept, Synthesis, Application”, edited by Newkome G. R, Wiley-VCH, 2001; and “Synthesis, Functionalization and Surface Treatment of Nanoparticles”, edited by Baraton M-I, ASP (Am. Sci. Pub.), Stevenson Ranch, Calif., 2003.

Over the past several years, polymer nanoparticles have also attracted increased attention not only in the technical fields such as catalysis, combinatorial chemistry, protein supports, magnets, and photonics, but also in the manufacture of rubber products such as tires. For example, nanoparticles can modify rubbers by uniformly dispersing throughout a host rubber composition as discrete particles. The physical properties of rubber such as moldability and tenacity can often be improved through such modifications.

The production and use of fluorescent labels in medicine and biology have grown rapidly and have been very profitable in the market. The availability of a new class of fluorescent markers offering clearly improved performance and safety is a strategic interest for this market. Today, biologists employing fluorescent techniques rely on dye molecules that have serious drawbacks. Particularly, many of these dye molecules are carcinogenic. Therefore there is a need for a safer, better performing material for use in the fluorescent/bio-optical market.

SUMMARY

A new class of fluorescent nanoparticles, and a method for their preparation is described and claimed.

As depicted in the example shown in FIG. 1, the nanoparticles described herein are each made up of a group or a collection of several polymer chains that are organized around a center 1. The polymer chains are linked together by a core formed from dialkenylbenzene(s). The polymer chains extend from the core 2 outwardly to form an intermediate layer 3. The intermediate layer 3 includes the monomer portions of the polymers that are not at the outer terminal end of the polymers (i.e., the intermediate layer includes monomer units that are not in the shell 4). It should be understood that the intermediate layer is not limited to a single monomer unit in each polymer chain, but may include several monomer units. Additionally, the intermediate layer may be separated into sublayers, and the sublayers may include blocks of various homopolymer or copolymer. For example a sublayer may include a block of randomized styrene-butadiene copolymer or a homopolymer such as polyisoprene or polystyrene. A shell layer or shell 4, is comprised of the monomer units or functionally or non-functionally initiated polymer chain heads at the outer terminal ends of each polymer. The shell layer 4 is the outermost portion of the nanoparticle.

The living polymers form micelles due to the aggregation of ionic chain ends and the chemical interactions of the hydrophobic polymer chains in hydrocarbon solvent. When the alkenylbenzene is added, the micelles become crosslinked and the stable nanoparticle is formed.

In one example, a fluorescent nanoparticle comprises (1) a core made from alkenylbenzene; (2) an intermediate layer; (3) a shell layer comprising the outer surface of the nanoparticle; and (4) a fluorescent portion that arises from the addition of a corresponding monomer with a structure represented by the following formula:

where L is a direct bond or a linker group, and F is any fluorescent moiety. The fluorescent portion is located in at least one of the following locations: the core, the intermediate layer, or the shell layer of the nanoparticle.

An example method of preparing such fluorescent nanoparticles includes: (i) preparing a living polymer with a fluorescent portion by a step selected from the group consisting of: (a) copolymerizing a fluorescent monomer with a monomer or monomers; (b) polymerizing a monomer or monomers with a fluorescent initiator; and (c) polymerizing a monomer to produce a living polymer, and subsequently adding a fluorescent monomer to the living polymer to create a fluorescent block; (ii) adding a crosslinking agent; and (iii) quenching the ionic chain ends with a proton source. After (i) but before (ii), the ionic chain ends of the polymers with fluorescent portions aggregate into micelles. The addition of the crosslinking agent causes the nanoparticle to form by producing a crosslinked core.

In yet another example, a fluorescent nanoparticle includes a core, an intermediate layer, and a shell layer. The intermediate and shell layers include ionic chain ends that extend from the intermediate layer into the core. The shell is the outermost layer of the nanoparticle. The core includes alkenylbenzene monomer units that have crosslinked the ionic chain ends of the intermediate layer. The alkenylbenzene monomers may have the same structure or may be a mixture of two or more different structures. A fluorescent portion is located in at least one of the intermediate or shell layers, or at the core. The fluorescent portion includes at least one fluorescent monomer with a structure represented by the following formula:


where L is a direct bond or a linker group, and F is a fluorescent moiety. The fluorescent monomer may be located at the core, the intermediate layer, or the shell layer.

The fluorescent nanoparticles can be used in rubber compositions.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an example diagram of a nanoparticle;

FIG. 2 is a transmission electron microscopy (TEM) photograph of fluorescent nanoparticles; and

FIG. 3 is the microscopy picture of a film containing the fluorescent nanoparticles.

 DETAILED DESCRIPTION

An exemplary fluorescent nanoparticle comprises a core including crosslinked alkenylbenzene monomers, an intermediate layer that includes polymer chains, and an outer shell layer that includes the head of the polymer chains. A fluorescent portion is located along the polymer chain in the intermediate layer, the shell, or at the core. It should be understood that the intermediate layer may have various thicknesses, i.e. the polymers may include one or many monomers. Preferably, the nanoparticle is less than 200 nm in diameter (expressed as a mean average diameter), more preferably less than about 100 nm, and most preferably less than about 50 nm. The nanoparticles are preferably spherical, though shape defects are acceptable, provided the nanoparticles generally retain their discrete nature with little or no polymerization between particles.

The fluorescent nanoparticles can be copolymerized in several ways. In one example, one or more monomers are polymerized with an initiator such as butyl lithium. The resulting ionic chain ends self-assemble into micelles around a center to form an aggregate core, while the hydrophobic polymer chains radiate out away from the ionic chain ends. A crosslinking agent, such as DVB, is then added along with a fluorescent monomer (or optionally the fluorescent monomer can be added in a separate step). The ionic chain ends within the aggregate core randomly react with both the DVB and fluorescent monomer to yield a crosslinked core containing fluorescent moieties. A proton source is used to quench the living polymer chains. Suitable proton sources are well known to those of skill in the art and include, but are not limited to, alcohols such as isopropanol.

In another example, one or more monomers are polymerized using a fluorescent initiator. The fluorescent initiator can be formed from a fluorescent monomer and an initiator such as butyl lithium. The resulting polymers have a fluorescent portion at one end. In a hydrocarbon solvent, the ionic chain ends aggregate into a micelle with the fluorescent portion on the outer surface. Then a crosslinking agent, such as DVB, is added to crosslink portions of the ionic chain ends of the micelle, thereby forming and stabilizing the core of the nanoparticle. A proton source is used to quench the living polymer chains.

In another example, one or more monomers and at least one fluorescent monomer are copolymerized using an initiator such as butyl lithium. The resultant living copolymers have a fluorescent portion within the chains. The ionic chain ends then self-assemble into micelles in a hydrocarbon solvent. A crosslinking agent, such as DVB, is added to crosslink portions of the ionic chain ends of the micelle, thereby forming and stabilizing the core of the nanoparticle. A proton source is used to quench the living polymer chains.

In another example, one or more monomers are polymerized using an initiator such as butyl lithium to a desired degree of polymerization. The resulting polymers are then copolymerized with one or more fluorescent monomers. This yields living copolymer chains with fluorescent portions within the chain. The living copolymer chains then self-assemble into micelles in a hydrocarbon solvent. A crosslinking agent, such as DVB, is added to crosslink portions of the ionic chain ends within the micelle, thereby forming and stabilizing the core of the nanoparticle. A proton source is used to quench the living polymer chains.

In variations of the above exemplary nanoparticle assembly methods, additional monomers can be copolymerized with the monomer, yielding various copolymers. Furthermore, the fluorescent monomer can be added at various stages in the copolymerization so as to control where in the polymer chain the fluorescent monomer is located.

Examples of the types of monomers that may be used to prepare the polymer chains of the nanoparticles include: styrene, t-butyl styrene, butadiene, isoprene, copolymers of a combination of these, or derivatives thereof. Mixtures of different polymers and copolymers are also possible in a single nanoparticle.

An exemplary fluorescent nanoparticle synthesis method comprises a multi-stage anionic polymerization. Multi-stage anionic polymerizations have been conducted to prepare block-copolymers, for example in U.S. Pat. No. 4,386,125, which is incorporated herein by reference.

A liquid hydrocarbon medium can function as the solvent, and may be selected from any suitable aliphatic hydrocarbon, alicyclic hydrocarbon, or mixture thereof with a proviso that it exists in liquid state during the preparation of the nanoparticles. Exemplary aliphatic hydrocarbons include, but are not limited to, pentane, isopentane, 2,2 dimethyl-butane, hexane, heptane, octane, nonane, decane, and the like. Exemplary alicyclic hydrocarbons include, but are not limited to, cyclopentane, methyl cyclopentane, cyclohexane, methyl cyclopentane, cycloheptane, cyclooctane, cyclononane, cyclodecane, and the like. Generally, aromatic hydrocarbons and polar solvents are not preferred as the liquid medium. In exemplified embodiments, the liquid hydrocarbon medium comprises hexane or cyclohexane.

In one example, the fluorescent nanoparticles are formed from polymers having a poly(alkyl-substituted styrene) block and a polymer block of fluorescent monomers having a structure represented by the formula shown below:


in which L is a direct bond or a linker group, and F is any fluorescent moiety.

For example, the fluorescent moiety F may be selected from the group consisting of perylene, phenanthrene, anthracene, naphthalene, pyrene, chrysene, naphthacene, and combinations thereof.

In one example, the —F group has a structure represented by the formula as shown below (pyrene):

The -L- group may be just a direct bond or any suitable divalent group, for example, methylene, ethylene, and propylene group. Preferably, the -L- group has a structure represented by the formula as shown below:


in which X comprises a heteroatom such as O, S, P(R2), Si(R2)2, Si(OR2)2 (where R2 is as defined below), and N (where N can be substituted such that the -L- group contains a tertiary amino group); and R1 is a straight or branched C1-C8 alkylene group.

In an example, the -L- group has a structure represented by the formula as shown below:

The fluorescent monomer may have, for example, a structure represented by the formula as shown below:

The fluorescent block may also optionally further comprise other monomers.

An example alkyl-substituted styrene block monomer of the example polymer may have a structure represented by the formula shown below:


in which m is an integer and 1≦m≦5, preferably m is 1 or 2; and R2 may be selected from saturated or unsaturated, substituted or unsubstituted, straight or branched, cyclic or acyclic C3-C8 alkyl groups.

Another exemplary alkyl-substituted styrene monomer comprises tert-butyl styrene (TbST) such as t-butyl styrene as shown below:

It is believed that the alkyl group in the alkyl-substituted styrene monomer lowers the overall solubility of the resulting living polymer in a selected liquid hydrocarbon medium thereby facilitating micelle self-assembly and nanoparticle formation.

In one example, the alkyl-substituted styrene monomer may be copolymerized with any suitable fluorescent comonomers; and as a result, the later formed nanoparticles will have a fluorescent intermediate later. Fluorescent comonomers for this purpose include, but are not limited to cinnamyl-O—CH2-pyrene. An exemplary polymerization of alkyl-substituted styrene monomers into a poly(alkyl-substituted styrene) block is initiated via addition of anionic initiators that are known in the art. For example, the anionic initiator can be selected from any known organolithium compounds. Suitable organolithium compounds are represented by the formula as shown below:
R(Li)x
wherein R is a hydrocarbyl group having 1 to x valence(s). R generally contains 1 to 20, preferably 2-8, carbon atoms per R group, and x is an integer of 1-4. Typically, x is 1, and the R group includes aliphatic groups and cycloaliphatic groups, such as alkyl, cycloalkyl, cycloalkylalkyl, alkylcycloalkyl, alkenyl, as well as aryl and alkylaryl groups.

Specific examples of R groups include, but are not limited to, alkyls such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-amyl, isoamyl, n-hexyl, n-octyl, n-decyl, and the like; cycloalkyls and alkylcycloalkyl such as cyclopentyl, cyclohexyl, 2,2,1-bicycloheptyl, methylcyclopentyl, dimethylcyclopentyl, ethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, ethylcyclohexyl, isopropylcyclohexyl, 4-butylcyclohexyl, and the like; cycloalkylalkyls such as cyclopentyl-methyl, cyclohexyl-ethyl, cyclopentyl-ethyl, methyl-cyclopentylethyl, 4-cyclohexylbutyl, and the like.

In selected examples, n-butyllithium, sec-butyllithium, tert-butyllithium, or a mixture thereof are used to initiate the polymerization of alkyl-substituted styrene monomers into a poly(alkyl-substituted styrene) block.

In one example, a fluorescent initiator may be used to initiate the polymerization of alkyl-substituted styrene monomers; and as a result, the later formed nanoparticles will have a fluorescent surface.

Examples of suitable fluorescent initiator include, but are not limited to, the following lithium compound:

Other examples of suitable fluorescent initiators may be obtained as taught in U.S. Published Application No. 2006/0036050, the entirety of which is incorporated herein by reference.

The polymerization of alkyl-substituted styrene monomers into a poly(alkyl-substituted styrene) block may last until a predetermined degree of polymerization is obtained. The degree of polymerization may be selected for particular applications. For example, a predetermined degree of polymerization of the poly(alkyl-substituted styrene) block may be broadly within the range of from about 1 to about 50, preferably within the range of from about 1 to about 25, more preferably within the range of from about 1 to about 10, and most preferably within the range of from about 1 to about 5.

The living polymer block that contains one or more fluorescent monomers may be copolymerized or crosslinked with a multiple vinyl-substituted aromatic hydrocarbon to form the desired fluorescent nanoparticles. The fluorescent nanoparticles preferably retain their discrete nature with little or no polymerization between each other. In an example embodiment, the fluorescent nanoparticles are substantially monodisperse and uniform in shape.

In another example, a mixture of multiple vinyl-substituted aromatic hydrocarbon and fluorescent monomer may be used to copolymerize with the poly(alkyl-substituted styrene) block, thus producing a crosslinked fluorescent core.

An exemplary multiple vinyl-substituted aromatic hydrocarbon has a formula as shown below:


in which p is an integer and 2≦p≦6, preferably, p is 2 or 3, more preferably p is 2, i.e. divinylbenzene (DVB).

In certain examples, the divinylbenzene may be selected from any one of the following isomers or any combination thereof:

Consequently, the fluorescent nanoparticles are formed from the micelles with a core including crosslinked alkyl-substituted styrene blocks and an intermediate layer including fluorescent blocks.

The polymerization reactions used to prepare the fluorescent nanoparticles may be terminated with a terminating agent. Suitable terminating agents are known to those skilled in the art and include, but are not limited to, alcohols such as methanol, ethanol, propanol, and isopropanol.

In embodiments, the molecular weight (grams/mole) of the fluorescent nanoparticles may be broadly within the range of from about 50,000 to about 100 million, preferably within the range of from about 100,000 to about 10 million.

Various rubber articles may be manufactured from the composition as described supra. References for this purpose may be made to, for example, U.S. Pat. No. 6,875,818, which is herein incorporated by reference.

In one example application, a composition including the fluorescent nanoparticles discussed herein may be sprayed or coated on a tire sidewall. The fluorescent property of the nanoparticles may function to improve traffic safety at night by increasing the visibility of the tires and the vehicle. Biological applications are also envisioned.

The following examples are included to provide additional guidance to those skilled in the art in practicing the claimed invention. The examples provided are merely representative of the work that contributes to the teaching of the present application. Accordingly, these examples are not intended to limit the invention, as defined in the appended claims, in any manner.

EXAMPLES Example 1 Preparation of Cinnamyl-O—CH2-pyrene Fluorescent Monomer

To a solution of 1-pyrene methanol (5 g, 21.5 mmol) in THF (150 mL) was added NaH (2 g, 50 mmol). After stirring for 30 min., cinnamyl chloride (4.3 g, 28.7 mmol) was added drop wise. After 2.5 h of reflux, the reaction was quenched with water and the two layers separated. The organic solution was washed with water (2×100 mL) followed by washing with brine (2×100 mL), dried over MgSO4 and concentrated to an orange oil. The product was purified by column chromatography (1:1, CH2Cl2:hexanes) to yield 5 g (67% yield). The structure was confirmed by 1H NMR analysis.

Example 2 Preparation of Fluorescent Nano Micelle Particles (FNMPs) with t-Butylstyrene

To a 10 oz. nitrogen purged bottle, cyclohexane (20 mL), t-butylstyrene (1.2 mL), oligomeric oxolanyl propane (OOPs) (0.03 mL, 1.6M) and butyl lithium (0.1 mL, 1.54M) were added. The bottle was placed into 80° C. water bath for 10 minutes. After cooling to 23° C., a charge of cinnamyl-O—CH2-pyrene (10 mL, 0.14M in cyclohexane) was added into the bottle. After continual cooling for 5 minutes, a charge of DVB (0.5 mL) was added to the mixture. The reaction proceeded for 1 hour, and then was then terminated by adding isopropanol (0.1 mL).

Example 3 Preparation of FNMPs with t-Butylstyrene

To a 10 oz. nitrogen purged bottle, hexane (20 mL), t-butylstyrene (1.2 mL), and butyl lithium (0.1 mL, 1.54M) were added. Then, the bottle was placed into an 80° C. water bath for 30 minutes. The bottle was then cooled and maintained at a temperature of 23° C. A mixture of cinnamyl-O—CH2-pyrene (10 mL, 0.14M in cyclohexane), DVB (0.5 mL) and t-butylstyrene (1 mL) was added to the bottle. The reaction proceeded at 23° C. for 2 hours, and was then terminated by adding isopropanol (0.1 mL).

Example 4 Preparation of FNMPs with t-Butylstyrene

To a 10 oz. nitrogen purged bottle, hexane (20 mL), t-butylstyrene (1.2 mL), and butyl lithium (0.1 mL, 1.54M) were added. Then, the bottle was placed into 80° C. water bath for 30 minutes and then cooled to 25° C. A mixture of cinnamyl-O—CH2-pyrene (10 mL, 0.14M in cyclohexane), DVB (0.5 mL), and t-butylstyrene (1 mL) was added to the bottle. After the reaction proceeded at 23° C. for 1 hour, t-butylstyrene (1 mL) was added to the bottle. After an additional 60 minutes, the reaction was terminated by adding isopropanol (0.5 mL).

Example 5 (Prospective): Preparation of FNMPs with Butadiene

To a 10 oz. nitrogen purged bottle, hexane (20 mL), butadiene (5 gr, 20% in hexane), oligomeric oxolanyl propane (OOPs) (0.03 mL, 1.6M solution) and butyl lithium (0.1 mL, 1.54M) would be added. The bottle would then be placed into 80° C. water bath for 10 minutes. After cooling to 23° C., a charge of cinnamyl-1-methylpyrene ether (10 mL, 0.14M in cyclohexane) would be added into the bottle. After continual cooling for 5 minutes, a charge of DVB (0.5 mL) would be added to the mixture. The reaction would proceed for 1 hour, and then would be terminated by adding isopropanol (0.1 mL).

Example 6 (Prospective): Preparation of FNMPs with Styrene Butadiene

To a 10 oz. nitrogen purged bottle, hexane (20 mL), styrene (1 gr, 30% in hexane), butadiene (5 gr, 20% in hexane), oligomeric oxolanyl propane (OOPs) (0.03 mL, 1.6M solution) and butyl lithium (0.1 mL, 1.54M) would be added. The bottle would be placed into 80° C. water bath for 10 minutes. After cooling to 23° C., a charge of cinnamyl-1-methylpyrene ether (10 mL, 0.14M in cyclohexane) would be added into the bottle. After continual cooling for 5 minutes, a charge of DVB (0.5 mL) would be added to the mixture. The reaction would proceed for 1 hour, and then would be terminated by adding isopropanol 0.1 mL).

Example 7 Characterization of Fluorescent Nano Micelle Particles (FNMPs)

A 1 mL portion of the Example 3 solution was diluted to about a 1×10−4 wt % solution in toluene. A drop of the diluted solution was then coated on a graphed copper micro-screen. After the solvent evaporated, the screen was exposed to RuO4 for about 5 minutes, and then examined by TEM. The image (see FIG. 2) shows that the FNMPs have a mean size of about 40 nm.

Example 8 Characterization of Fluorescent Nano Micelle Particles (FNMPs)

A 5 mL aliquot was taken from the Example 3 reaction and added to an aluminum pan. After the solvent evaporated, a film of about 0.1 mm thickness resulted. The characterization was performed using an Olympus-BH2 microscope equipped with a Polaroid camera. The polymer film was examined under a UV light. The film showed fluorescence under green light (˜450 to 510 nm). As shown in FIG. 2, the film was entirely glowing as compared to the background. The experiment indicated that the desired nano-sized materials with fluorescent properties were produced.

While the invention has been illustrated and described by way of examples, it is not intended to be limited to the details shown, since various modifications and substitutions can be made without departing in any way from the spirit of the present invention. As such, further modifications and equivalents of the invention herein disclosed may occur to persons skilled in the art using no more than routine experimentation, and all such modifications and equivalents are believed to be within the spirit and scope of the invention as defined by the following claims.

Claims

1. A fluorescent nanoparticle comprising:

(a) a core comprising at least one alkenylbenzene monomer;
(b) an intermediate layer comprising polymer chains;
(c) a shell layer comprising an outer surface of the nanoparticle; and
(d) at least one fluorescent portion bonded to the nanoparticle;
the fluorescent portion arising from the addition of a corresponding monomer with a structure represented by the following formula:
wherein L is a direct bond or a linker group, and F is any fluorescent moiety;
wherein the fluorescent portion is a monomer-contributed unit located in at least one of the following locations: the core, the intermediate layer, or the shell layer of the nanoparticle.

2. The fluorescent nanoparticle of claim 1, wherein the polymer chains are selected from the group consisting of: polystyrene, polybutadiene, polyisoprene, copolymers of a combination of styrene, butadiene, or isoprene, derivatives thereof, or mixtures thereof.

3. The fluorescent nanoparticle according to claim 1, in which the fluorescent moiety F is selected from the group consisting of pyrene, perylene, phenanthrene, anthracene, naphthalene, and combinations thereof.

4. The fluorescent nanoparticle according to claim 1, in which the fluorescent moiety F has formula of:

5. The fluorescent nanoparticle of claim 1, in which the fluorescent moiety F has a formula of:

6. The fluorescent nanoparticle of claim 1, in which the linker group L is:

wherein X comprises a heteroatom; and R1 is a straight or branched C1-C8 alkylene group.

7. The fluorescent nanoparticle of claim 1, in which the linker group L is:

8. The fluorescent nanoparticle of claim 1, in which the at least one fluorescent portion contains one or more monomers-contributed units with a formula of:

9. The fluorescent nanoparticle of claim 1, in which the at least one alkenylbenzene monomer has a formula of:

wherein m is an integer and 1≦m≦5; and R2 is selected from saturated or unsaturated, substituted or unsubstituted, straight or branched, cyclic or acyclic C3-C8 alkyl groups.

10. The fluorescent nanoparticle of claim 1, in which the at least one alkenylbenzene monomer has a formula of:

11. The fluorescent nanoparticle of claim 1, wherein the shell includes one or more fluorescent portions and the one or more fluorescent portions comprises residues of a fluorescent initiator.

12. The fluorescent nanoparticle of claim 11, in which the fluorescent initiator has a formula of:

13. The fluorescent nanoparticle of claim 1, wherein the core is crosslinked using a multiple vinyl-substituted aromatic hydrocarbon having a formula of:

wherein p is an integer and 2≦p≦6.

14. The fluorescent nanoparticle of claim 13, in which the multiple vinyl-substituted aromatic hydrocarbon is selected from one of the following isomers or any combination thereof:

15. The fluorescent nanoparticle of claim 1, which has a weight average molecular weight of from about 50,000 to about 100 million.

16. The fluorescent nanoparticle of claim 1, which has a generally spherical shape with a mean average diameter of less than about 100 nm.

17. The fluorescent nanoparticle of claim 1, wherein the fluorescent portion is located along a polymer chain in the intermediate layer.

18. The fluorescent nanoparticle of claim 1, wherein the fluorescent portion is located in the core.

19. The fluorescent nanoparticle of claim 1, wherein the nanoparticle has a diameter of less than about 200 nm.

20. A fluorescent nanoparticle comprising:

a core, an intermediate layer, and a shell layer; the intermediate and shell layers include polymer chains extending from the intermediate layer into the shell layer, the shell being the outermost layer of the nanoparticle; the core including alkenylbenzene monomers, the alkenylbenzene monomers having the same structure or being a mixture of two or more different structures; the alkenylbenzene monomers crosslinking living polymer chain ends of the polymer chains of the intermediate layer; a fluorescent portion bonded to at least one of the intermediate or shell layers, or the core; the fluorescent portion including at least one fluorescent monomer-contributed unit with a structure represented by the following formula:
wherein L is a direct bond or a linker group, and F is a fluorescent moiety.

21. The fluorescent nanoparticle of claim 20, wherein blocks of the polymer chains in the intermediate and shell layers are more soluble in a hydrocarbon solvent than blocks of the polymer chains in the intermediate layer that are nearer the core.

22. The fluorescent nanoparticle of claim 20, wherein the intermediate layer comprises a poly(conjugated diene).

23. The fluorescent nanoparticle of claim 20, in which the fluorescent portion comprises residues of a fluorescent initiator.

24. The fluorescent nanoparticle of claim 20, wherein the nanoparticle has a diameter of less than about 200 nm.

Referenced Cited
U.S. Patent Documents
2531396 November 1950 Carter et al.
3598884 August 1971 Wei et al.
3725505 April 1973 O'Malley
3793402 February 1974 Owens
3840620 October 1974 Gallagher
3972963 August 3, 1976 Schwab et al.
4233409 November 11, 1980 Bulkley
4247434 January 27, 1981 Vanderhoff et al.
4326008 April 20, 1982 Rembaum
4386125 May 31, 1983 Shiraki et al.
4463129 July 31, 1984 Shinada et al.
4543403 September 24, 1985 Isayama et al.
4598105 July 1, 1986 Weber et al.
4602052 July 22, 1986 Weber et al.
4659790 April 21, 1987 Shimozato et al.
4717655 January 5, 1988 Fulwyler
4725522 February 16, 1988 Breton et al.
4764572 August 16, 1988 Bean, Jr.
4773521 September 27, 1988 Chen
4774189 September 27, 1988 Schwartz
4788254 November 29, 1988 Kawakubo et al.
4829130 May 9, 1989 Licchelli et al.
4829135 May 9, 1989 Gunesin et al.
4837274 June 6, 1989 Kawakubo et al.
4837401 June 6, 1989 Hirose et al.
4861131 August 29, 1989 Bois et al.
4870144 September 26, 1989 Noda et al.
4871814 October 3, 1989 Gunesin et al.
4904730 February 27, 1990 Moore et al.
4904732 February 27, 1990 Iwahara et al.
4906695 March 6, 1990 Blizzard et al.
4920160 April 24, 1990 Chip et al.
4942209 July 17, 1990 Gunesin
5036138 July 30, 1991 Stamhuis et al.
5066729 November 19, 1991 Stayer, Jr. et al.
5073498 December 17, 1991 Schwartz et al.
5075377 December 24, 1991 Kawabuchi et al.
5120379 June 9, 1992 Noda et al.
5130377 July 14, 1992 Trepka et al.
5169914 December 8, 1992 Kaszas et al.
5194300 March 16, 1993 Cheung
5219945 June 15, 1993 Dicker et al.
5227419 July 13, 1993 Moczygemba et al.
5237015 August 17, 1993 Urban
5241008 August 31, 1993 Hall
5247021 September 21, 1993 Fujisawa et al.
5256736 October 26, 1993 Trepka et al.
5262502 November 16, 1993 Fujisawa et al.
5290873 March 1, 1994 Noda et al.
5290875 March 1, 1994 Moczygemba et al.
5290878 March 1, 1994 Yamamoto et al.
5329005 July 12, 1994 Lawson et al.
5331035 July 19, 1994 Hall
5336712 August 9, 1994 Austgen, Jr. et al.
5362794 November 8, 1994 Inui et al.
5395891 March 7, 1995 Obrecht et al.
5395902 March 7, 1995 Hall
5399628 March 21, 1995 Moczygemba et al.
5399629 March 21, 1995 Coolbaugh et al.
5405903 April 11, 1995 Van Westrenen et al.
5421866 June 6, 1995 Stark-Kasley et al.
5436298 July 25, 1995 Moczygemba et al.
5438103 August 1, 1995 DePorter et al.
5447990 September 5, 1995 Noda et al.
5462994 October 31, 1995 Lo et al.
5514734 May 7, 1996 Maxfield et al.
5514753 May 7, 1996 Ozawa et al.
5521309 May 28, 1996 Antkowiak et al.
5525639 June 11, 1996 Keneko et al.
5527870 June 18, 1996 Maeda et al.
5530052 June 25, 1996 Takekoshi et al.
5580925 December 3, 1996 Iwahara et al.
5587423 December 24, 1996 Brandstetter et al.
5594072 January 14, 1997 Handlin, Jr. et al.
5614579 March 25, 1997 Roggeman et al.
5627252 May 6, 1997 De La Croi Habimana
5686528 November 11, 1997 Wills et al.
5688856 November 18, 1997 Austgen, Jr. et al.
5700897 December 23, 1997 Klainer et al.
5707439 January 13, 1998 Takekoshi et al.
5728791 March 17, 1998 Tamai et al.
5733975 March 31, 1998 Aoyama et al.
5739267 April 14, 1998 Fujisawa et al.
5742118 April 21, 1998 Endo et al.
5763551 June 9, 1998 Wunsch et al.
5773521 June 30, 1998 Hoxmeier et al.
5777037 July 7, 1998 Yamanaka et al.
5811501 September 22, 1998 Chiba et al.
5834563 November 10, 1998 Kimura et al.
5847054 December 8, 1998 McKee et al.
5849847 December 15, 1998 Quirk
5855972 January 5, 1999 Kaeding
5883173 March 16, 1999 Elspass et al.
5891947 April 6, 1999 Hall et al.
5897811 April 27, 1999 Lesko
5905116 May 18, 1999 Wang et al.
5910530 June 8, 1999 Wang et al.
5955537 September 21, 1999 Steininger et al.
5986010 November 16, 1999 Clites et al.
5994468 November 30, 1999 Wang et al.
6011116 January 4, 2000 Aoyama et al.
6020446 February 1, 2000 Okamoto et al.
6025416 February 15, 2000 Proebster et al.
6025445 February 15, 2000 Chiba et al.
6060549 May 9, 2000 Li et al.
6060559 May 9, 2000 Feng et al.
6087016 July 11, 2000 Feeney et al.
6087456 July 11, 2000 Sakaguchi et al.
6106953 August 22, 2000 Zimmermann et al.
6117932 September 12, 2000 Hasegawa et al.
6121379 September 19, 2000 Yamanaka et al.
6127488 October 3, 2000 Obrecht et al.
6147151 November 14, 2000 Fukumoto et al.
6180693 January 30, 2001 Tang et al.
6191217 February 20, 2001 Wang et al.
6197849 March 6, 2001 Zilg et al.
6204354 March 20, 2001 Wang et al.
6225394 May 1, 2001 Lan et al.
6252014 June 26, 2001 Knauss
6255372 July 3, 2001 Lin et al.
6268451 July 31, 2001 Faust et al.
6277304 August 21, 2001 Wei et al.
6348546 February 19, 2002 Hiiro et al.
6359075 March 19, 2002 Wollum et al.
6379791 April 30, 2002 Cernohous et al.
6383500 May 7, 2002 Wooley et al.
6395829 May 28, 2002 Miyamoto et al.
6420486 July 16, 2002 DePorter et al.
6437050 August 20, 2002 Krom et al.
6441090 August 27, 2002 Demirors et al.
6448353 September 10, 2002 Nelson et al.
6489378 December 3, 2002 Sosa et al.
6506567 January 14, 2003 Makino et al.
6524595 February 25, 2003 Perrier et al.
6573313 June 3, 2003 Li et al.
6573330 June 3, 2003 Fujikake et al.
6598645 July 29, 2003 Larson
6649702 November 18, 2003 Rapoport et al.
6663960 December 16, 2003 Murakami et al.
6689469 February 10, 2004 Wang et al.
6693746 February 17, 2004 Nakamura et al.
6706813 March 16, 2004 Chiba et al.
6706823 March 16, 2004 Wang et al.
6727311 April 27, 2004 Ajbani et al.
6737486 May 18, 2004 Wang
6750297 June 15, 2004 Yeu et al.
6759464 July 6, 2004 Ajbani et al.
6774185 August 10, 2004 Lin et al.
6777500 August 17, 2004 Lean et al.
6780937 August 24, 2004 Castner
6835781 December 28, 2004 Kondou et al.
6858665 February 22, 2005 Larson
6861462 March 1, 2005 Parker et al.
6872785 March 29, 2005 Wang et al.
6875818 April 5, 2005 Wang
6908958 June 21, 2005 Maruyama et al.
6956084 October 18, 2005 Wang et al.
7056840 June 6, 2006 Miller et al.
7071246 July 4, 2006 Xie et al.
7112369 September 26, 2006 Wang et al.
7179864 February 20, 2007 Wang
7193004 March 20, 2007 Weydert et al.
7205370 April 17, 2007 Wang et al.
7217775 May 15, 2007 Castner
7238751 July 3, 2007 Wang et al.
7244783 July 17, 2007 Lean et al.
7291394 November 6, 2007 Winkler et al.
7347237 March 25, 2008 Xie et al.
7408005 August 5, 2008 Zheng et al.
20010053813 December 20, 2001 Konno et al.
20020007011 January 17, 2002 Konno et al.
20020045714 April 18, 2002 Tomalia et al.
20020095008 July 18, 2002 Heimrich et al.
20020144401 October 10, 2002 Nogueroles Vines et al.
20030004250 January 2, 2003 Ajbani et al.
20030032710 February 13, 2003 Larson
20030124353 July 3, 2003 Wang et al.
20030130401 July 10, 2003 Lin et al.
20030149185 August 7, 2003 Wang et al.
20030198810 October 23, 2003 Wang et al.
20030225190 December 4, 2003 Borbely et al.
20040033345 February 19, 2004 Dubertret et al.
20040059057 March 25, 2004 Swisher et al.
20040127603 July 1, 2004 Lean et al.
20040143064 July 22, 2004 Wang
20040198917 October 7, 2004 Castner
20050101743 May 12, 2005 Stacy et al.
20050182158 August 18, 2005 Ziser et al.
20050192408 September 1, 2005 Lin et al.
20050197462 September 8, 2005 Wang et al.
20050203248 September 15, 2005 Zheng et al.
20050215693 September 29, 2005 Wang et al.
20050228074 October 13, 2005 Wang et al.
20050282956 December 22, 2005 Bohm et al.
20060084722 April 20, 2006 Lin et al.
20060173115 August 3, 2006 Wang et al.
20060173130 August 3, 2006 Wang et al.
20060235128 October 19, 2006 Bohm et al.
20070135579 June 14, 2007 Obrecht et al.
20070142550 June 21, 2007 Wang et al.
20070142559 June 21, 2007 Wang et al.
20070149649 June 28, 2007 Wang et al.
20070161754 July 12, 2007 Bohm et al.
20070185273 August 9, 2007 Hall et al.
20070196653 August 23, 2007 Hall et al.
20080145660 June 19, 2008 Wang et al.
20080149238 June 26, 2008 Kleckner et al.
20080160305 July 3, 2008 Wang et al.
20080286374 November 20, 2008 Wang et al.
20080305336 December 11, 2008 Wang et al.
20090005491 January 1, 2009 Warren et al.
20090048390 February 19, 2009 Wang et al.
20090054554 February 26, 2009 Wang et al.
Foreign Patent Documents
2127919 March 1995 CA
3434983 April 1986 DE
4241538 June 1994 DE
0143500 June 1985 EP
0255170 February 1988 EP
0265142 April 1988 EP
0322905 July 1989 EP
0352042 January 1990 EP
0472344 February 1992 EP
0540942 May 1993 EP
0590491 April 1994 EP
0742268 November 1996 EP
1031605 August 2000 EP
1099728 May 2001 EP
1134251 September 2001 EP
1273616 June 2002 EP
1321489 June 2003 EP
1783168 May 2007 EP
01279943 January 1989 JP
2191619 July 1990 JP
2196893 August 1990 JP
05132605 May 1993 JP
7011043 January 1995 JP
08199062 August 1996 JP
2000-514791 November 2000 JP
2003-095640 April 2003 JP
2006-072283 March 2006 JP
2006-106596 April 2006 JP
2007-304409 November 2007 JP
91/04992 April 1991 WO
97/04029 February 1997 WO
9853000 November 1998 WO
0075226 December 2000 WO
01/87999 November 2001 WO
02/31002 April 2002 WO
02/081233 October 2002 WO
02/100936 December 2002 WO
03/032061 April 2003 WO
03085040 October 2003 WO
2004/058874 July 2004 WO
2006/069793 July 2006 WO
2008/079276 July 2008 WO
2008/079807 July 2008 WO
2009/006434 January 2009 WO
Other references
  • Star Polymers by Immobilizing Functional Block Copolymers, by Koji Ishizu, Tokyo Institute of Technology, Meguro-ku, Tokyo, Japan, Star and Hyperbranched Polymers, 1999, ISBN 0-8247-1986-7.
  • Formation of Worm-like Micelles from a Polystyrene-Polybutadiene-Polystyrene Block Copolymer in Ethyl Acetate, Canham et al., J.C.S. Faraday I, 1980, 76, 1857-1867.
  • Anomalous Behaviour of Solutions of Styrene-Butadiene Block Copolymers in Some Solvents, Tuzar et al., Makromol. Chem. 178, 22743-2746, 1977.
  • Association of Block Copolymers in Selective Solvents, 1 Measurements on Hydrogenated Poly(styrene-isoprene) in Decane and in trans-Decalin, Mandema et al., Makromol. Chem. 180, 1521-1538, 1979.
  • Light-Scattering Studies of a Polystyrene-Poly(methyl methacrylate) Two-Blcok Copolymer in Mixed Solvents, Utiyama et al. Macromolecules vol. 7, No. 4, Jul.-Aug. 1974.
  • Greenwod, N.N.; Earnshaw, A., Chemistry of the Elements, pp. 1126-1127, Pergaroen Press, New York 1984.
  • Kink-Block and Gauche-Block Structures of Bimolecular Films, Gehard Lagaly, Chem. Int. Ed. Engl. vol. 15 (1976) No. 10, pp. 575-586.
  • Linear Viscoelasticity of Disordered Polystyrene-Polyisoprene . . . Layered-Silicate Nanocomposites, J. Ren, Dept. of Chem Eng. Univ. of Houston, Macromol. 2000, pp. 3739-3746.
  • Rheology of End-Tethered Polymer Layered Silicate Nanocomposites, R. Krishnamoorti et al., Macromol. 1997, 30, 4097-4102.
  • Rheology of Nanocomposites Based on Layered Silicates and Polyamide-12, B. Hoffman et al., Colloid Polm. Sci. 278:629-636 (2000).
  • Quaternary Ammonium Compounds, Encyclopedia of Chem Tech., 4th Ed. vol. 20, 1996, Wiley & Sons, pp. 739-767.
  • Dendritic Macromolecules: Synthesis of Starburst Dendrimers, Donald A. Tomalia et al., Macromolecules vol. 19, No. 9, 1986, contribution from Functional Polymers/Processes and the Analytical Laboratory, Dow Chemical, Midland, MI 48640, pp. 2466-2468.
  • Preparation and Characterization of Heterophase Blends of Polycaprolactam and Hydrogenated Polydienes, David F. Lawson et al., pp. 2331-2351, Central Research Labs., The Firestone Tire and Rubber Col, Akron, OH 44317, Journal of Applied Polymer Science, vol. 39, 1990 John Wiliey & Sons, Inc.
  • R.P. Quirk and S.C. Galvan, Macromolecules, 34, 1192-1197 (2001).
  • M. Moller, J.P. Spaz, A. Roescher, S. Mobmer, S.T. Selvan, H.A. Klok, Macromol. Symp. 117, 207-218 (1997).
  • T. Cosgrove, J.S. Phipps, R.M. Richardson, Macromolecules, 26, 4363-4367 (1993).
  • S. Mossmer, J.P. Spatz, M.Moller, T. Aberle, J. Schmidt, W. Burchard, Macromol. 33, 4791-4798 (2000).
  • Ultrahydrophobic and Ultrayophobic Surfaces: Some Comments and Examples, Wei Chen et al., The ACS Journal of Surfaces and Colloids, May 11, 1999, vol. 15, No. 10, pp. 3395-3399, Polymer Science and Engineering Dept., Univ. of MA, Amherst, MA 01003.
  • Super-Repellent Composite Fluoropolymer Surfaces, S.R. Coulson, I. Woodward, J.P.S. Badyal, The Journal of Physical Chemistry B, vol. 104, No. 37, Sep. 21, 2000, pp. 8836-8840, Dept. of Chemistry, Science Laboratories, Durham University, Durham, DH1 3LE, England, U.K.
  • Transformation of a Simple Plastic into a Superhydrophobic Surface, H. Yildirim Erbil et al., Science vol. 299, Feb. 28, 2003, pp. 1377-1380.
  • Reaction of Primary Aliphatic Amines with Maleic Anhydride, Lester E. Coleman et al., J. Org. Chem., 24, 185, 1959, pp. 135-136.
  • Synthesis, Thermal Properties and Gas Permeability of Poly (N-n-alkylmaleimide)s, A. Matsumoto et al., Polymer Journal vol. 23, No. 3, 1991, pp. 201-209.
  • Simultaneous TA and MS Analysis of Alternating Styrene-Malei Anhydride and Styrene-Maleimide Copolymers, Thermochim. Acta, 277, 14, 1996.
  • Synthesis and Photocrosslinking of Maleimide-Type Polymers, Woo-Sik Kim et al., Macromol. Rapid Commun., 17, 835, 1996, pp. 835-841.
  • Polysulfobetaines and Corresponding Cationic Polymers. IV. Synthesis and Aqueous Solution Properties of Cationic Poly (MIQSDMAPM), Wen-Fu Lee et al., J. Appl. Pol. Sci. vol. 59, 1996, pp. 599-608.
  • Chemical Modification of Poly (styrene-co-maleic anhydride) with Primary N-Alkylamines by Reactive Extrusion, I Vermeesch et al., J. Applied Polym. Sci., vol. 53, 1994, pp. 1365-1373.
  • Vulcanization Agents and Auxiliary Materials, Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd Ed., Wiley Interscience, NY, 1982, vol. 22, pp. 390-402.
  • Dialkylimidazolium Chloroaluminate Melts: A New Class of Room-Temperature Ionic Liquids of Electrochemistry, Spectroscopy, and Synthesis. J.S. Wilkes, J.A. Levisky, B.A. Wilson, Inorg. Chem. 1982, 21, pp. 1263-1264.
  • Polymer-m-Ionic-Liquid Electrolytes C. Tiyapiboonchaiya, D.R. MacFarlane, J. Sun, M. Forsyth, Micromol. Chem. Phys., 2002, 203, pp. 1906-1911.
  • EXAFS Investigations of the Mechanism of Facilitated Ion Transfer into a Room-Temperature Ionic Liquid. M. Jensen, J.A. Dzielawa, P. Rickert, M.L. Dietz, Jacs, 2002, 124, pp. 10664-10665.
  • Structure of molten 1,3-dimethylimidazolium chloride using neutron diffraction.C. Hardacre, J.D. Holbrey, S.E.J. McMath, D.T. Bowron, A.K. Soper, J. Chem. Physics, 2003, 118(1), pp. 273-278.
  • Reverse Atom Transfer Radical Polymerization of Methyl Methacrylate in Room-Temperature Inoic Liqquids, H. Ma, X. Chen, Q-F. Zhou, J. Polym. Sci., A. Polym. Chem. 2003, 41, pp. 143-151.
  • Non-Derby Relaxations in Disordered Ionic Solids, W. Dieterich, P. Maass, Chem. Chys. 2002, 284, pp. 439-467.
  • Polymer Layered Silicate Nanocomposites, Giannelis E.P. Advanced Materials vol. 8, No. 1, Jan. 1, 1996, pp. 29-35.
  • A Review of Nanocomposites 2000, J.N. Hay, S. J. Shaw.
  • “Dendrimers and Dendrons, Concept, Synthesis, Application”, edited by Newkome G.R, Wiley-VCH, 2001, pp. 45, 191-310.
  • “Synthesis, Functionalization and Surface Treatment of Nanoparticles”, edited by Baraton M-I, ASP (Am. Sci. Pub.), Stevenson Ranch, California, 2003, pp. 51-52, 174-208.
  • Akashi, Mitsuru et al., “Synthesis and Polymerization of a Styryl Terminated Oligovinylpyrrolidone Macromonomer”, Die Angewandte Makromolekulare Chemie, 132, pp. 81-89 (1985).
  • Alexandridis, Paschalis et al., “Amphiphilic Block Copolymers: Self-Assembly and Applications”, Elsevier Science B.V., pp. 1-435 (2000).
  • Allgaier, Jurgen et al., “Synthesis and Micellar Properties of PS-PI Block Copolymers of Different Architecture”, ACS Polym. Prepr. (Div Polym. Chem.), vol. 37, No. 2, pp. 670-671 (1996).
  • Antonietti, Markus et al., “Determination of the Micelle Architecture of Polystyrene/Poly(4-vinylpyridine) Block Copolymers in Dilute Solution”, Macromolecules, 27, pp. 3276-3281 (1994).
  • Antonietti, Markus et al., “Novel Amphiphilic Block Copolymers by Polymer Reactions and Their Use for Solubilization of Metal Salts and Metal Colloids”, Macromolecules, 29, pp. 3800-3806 (1996).
  • Bahadur, Pratap, “Block copolymers- Their microdomain formation (in solid state) and surfactant behavior (in solution)”, Current Science, vol. 80, No. 8, pp. 1002-1007, Apr. 25, 2001.
  • Batzilla, Thomas et al., “Formation of intra- and intermolecular crosslinks in the radical crosslinking of poly(4-vinylstyrene)”, Makromol. Chem., Rapid Commun. 8, pp. 261-268 (1987).
  • Bauer, B.J. et al., “Synthesis and Dilute-Solution Behavior of Model Star-Branched Polymers”, Rubber Chemistry and Technology, vol. 51, pp. 406-436 (1978).
  • Berger, G. et al., “Mutual Termination of Anionic and Cationic ‘Living’ Polymers”, Polymer Letters, vol. 4, pp. 183-186 (1966).
  • Bohm, Georg et al., “Emerging materials: technology for new tires and other rubber products”, Tire Technology International, 2006 (4 pp.).
  • Bradley, John S., “The Chemistry of Transition Metal Colloids”, Clusters and Colloids: From Theory to Applications, Chapter 6, Weinheim, VCH, pp. 459-544 (1994).
  • Bronstein, Lyudmila M. et al., “Synthesis of Pd-, Pt-, and Rh-containing polymers derived from polystyrene-polybutadiene block copolymers; micellization of diblock copolymers due to complexation”, Macromol. Chem. Phys., 199, pp. 1357-1363 (1998).
  • Calderara, Frederic et al., “Synthesis of chromophore-labelled polystyrene/poly(ethylene oxide) diblock copolymers”, Makromol. Chem., 194, pp. 1411-1420 (1993).
  • Chen, Ming-Qing et al., “Graft Copolymers Having Hydrophobic Backbone and Hydrophilic Branches. XXIII. Particle Size Control of Poly(ethylene glycol)- Coated Polystyrene Nanoparticles Prepared by Macromonomer Method”, Journal of Polymer Science: Part A: Polymer Chemistry, vol. 37, pp. 2155-2166 (1999).
  • Edmonds, William F. et al., “Disk Micelles from Nonionic Coil- Coil Diblock Copolymers”, Macromolecules, vol. 39, pp. 4526-4530 (May 28, 2006).
  • Ege, Seyhan, Organic Chemistry Structure and Reactivity, 3rd Edition, p. 959, 1994.
  • Eisenberg, Adi, “Thermodynamics, Kinetics, and Mechanisms of the Formation of Multiple Block Copolymer Morphologies”, Polymer Preprints, vol. 41, No. 2, pp. 1515-1516 (2000).
  • Erhardt, Rainer et al., Macromolecules, vol. 34, No. 4, pp. 1069-1075 (2001).
  • Eschway, Helmut et al., “Preparation and Some Properties of Star-Shaped Polymers with more than Hundred Side Chains”, Die Makromolekulare Chemie 173, pp. 235-239 (1973).
  • Eschway, Helmut et al., “Star polymers from styrene and divinylbenzene”, Polymer, vol. 16, pp. 180-184 (Mar. 1975).
  • Fendler, Janos H., “Nanoparticles and Nanostructured Films: Preparation, Characterization and Applications”, Wiley-VCH, pp. 1-468 (1998).
  • Garcia, Carlos B. et al., “Self-Assembly Approach toward Magnetic Silica-Type Nanoparticles of Different Shapes from Reverse Block Copolymer Mesophases”, J. Am. Chem. Soc., vol. 125, pp. 13310-13311 (2003).
  • Guo, Andrew et al., “Star Polymers and Nanospheres from Cross-Linkable Diblock Copolymers”, Macromolecules, vol. 29, pp. 2487-2493, Jan. 17, 1996.
  • Hamley, Ian W., “The Physics of Block Copolymers”, Oxford Science Publication: Oxford, Chapters 3 and 4, pp. 131-265, (1998).
  • Ishizu, Koji et al., “Synthesis of Star Polymer with Nucleus of Microgel”, Polymer Journal, vol. 12, No. 6, pp. 399-404 (1980).
  • Ishizu, Koji et al., “Core-Shell Type Polymer Microspheres Prepared from Block Copolymers”, Journal of Polymer Science: Part C: Polymer Letters, vol. 26, pp. 281-286, 1988.
  • Ishizu, Koji, “Synthesis and Structural Ordering of Core-Shell Polymer Microspheres”, Prog. Polym. Sci., vol. 23, pp. 1383-1408, 1998.
  • Ishizu, Koji, “Structural Ordering of Core Crosslinked Nanoparticles and Architecture of Polymeric Superstructures”, ACS Polym. Prepr. (Div Polym Chem) vol. 40, No. 1, pp. 456-457 (1999).
  • Liu, Guojun et al., “Diblock Copolymer Nanofibers”, Macromolecules, 29, pp. 5508-5510 (1996).
  • Liu, T. et al., “Formation of Amphiphilic Block Copolymer Micelles in Nonaqueous Solution”, Amphiphilic Block Copolymers: Self-Assembly and Applications, Elsevier Science B.V., pp. 115-149 (2000).
  • Ma, Qinggao et al., “Entirely Hydrophilic Shell Cross-Linked Knedel-Like (SCK) Nanoparticles”, Polymer Preprints, vol. 41, No. 2, pp. 1571-1572 (2000).
  • Mayer, A.B.R. et al., “Transition metal nanoparticles protected by amphiphilic block copolymers as tailored catalyst systems”, Colloid Polym. Sci., 275, pp. 333-340 (1997).
  • Mi, Yongli et al., “Glass transition of nano-sized single chain globules”, Polymer 43, Elsevier Science Ltd., pp. 6701-6705 (2002).
  • Nace, Vaughn M., “Nonionic Surfactants: Polyoxyalkylene Block Copolymers”, Surfactant Science Series, vol. 60, pp. 1-266 (1996).
  • O'Reilly, Rachel K. et al., “Cross-linked block copolymer micelles: functional nanostructures of great potential and versatility”, Chem. Soc. Rev., vol. 35, pp. 1068-1083, Oct. 2, 2006.
  • Okay, Oguz et al., “Steric stabilization of reactive microgels from 1,4-divinylbenzene”, Makormol. Chem., Rapid Commun., vol. 11, pp. 583-587 (1990).
  • Okay, Oguz et al., “Anionic Dispersion Polymerization of 1, 4-Divinylbenzene”, Macromolecules, 23, pp. 2623-2628 (1990).
  • Oranli, Levent et al., “Hydrodynamic studies on micellar solution of styrene-butadiene block copolymers in selective solvents”, Can. J. Chem., vol. 63, pp. 2691-2696, 1985.
  • Piirma, Irja, “Polymeric Surfactants”, Surfactant Science Series, vol. 42, pp. 1-289 (1992).
  • Pispas, S. et al., “Effect of Architecture on the Micellization Properties of Block Copolymers: A2B Miktoarm Stars vs AB Diblocks”, Macromolecules, vol. 33, pp. 1741-1746, Feb. 17, 2000.
  • Price, Colin, “Colloidal Properties of Block Copolymers”, Applied Science Publishers Ltd., Chapter 2, pp. 39-80 (1982).
  • Rager, Timo et al., “Micelle formation of poly(acrylic acid)- block-poly(methyl methacrylate) block copolymers in mixtures of water with organic solvents”, Macromol. Chem. Phys., 200, No. 7, pp. 1672-1680 (1999).
  • Rein, David H. et al., “Kinetics of arm-first star polymers formation in a non-polar solvent”, Macromol. Chem. Phys., vol. 199, pp. 569-574 (1998).
  • Rempp, Paul et al., “Grafting and Branching of Polymers”, Pure Appl. Chem., vol. 30, pp. 229-238 (1972).
  • Riess, Gerard et al., “Block Copolymers”, Encyclopedia of Polymer Science and Engineering, vol. 2, pp. 324-434 (1985).
  • Riess, Gerard, “Micellization of block copolymers”, Prog. Polym. Sci., vol. 28, pp. 1107-1170, Jan. 16, 2003.
  • Saito, Reiko et al., “Synthesis of microspheres with ‘hairy-ball’ structures from poly (styrene-b-2-vinyl pyridine) diblock copolymers”, Polymer, vol. 33, No. 5, pp. 1073-1077, 1992.
  • Saito, Reiko et al., “Synthesis of Microspheres with Microphase-Separated Shells”, Journal of Polymer Science: Part A: Polymer Chemistry, vol. 38, pp. 2091-2097 (2000).
  • Serizawa, Takeshi et al., “Transmission Electron Microscopic Study of Cross-Sectional Morphologies of Core-Corona Polymeric Nanospheres”, Macromolecules, 33, pp. 1759-1764 (2000).
  • Stepanek, Moroslav et al. “Time-Dependent Behavior of Block Polyelectrolyte Micelles in Aqueous Media Studied by Potentiometric Titrations, QELS and Fluoroetry”, Langmuir, Vo. 16, No. 6, pp. 2502-2507 (2000).
  • Thurmond II, K. Bruce et al., “Water-Soluble Knedel-like Structures: The Preparation of Shell-Cross-Linked Small Particles”, J. Am. Chem. Soc., vol. 118, pp. 7239-7240 (1996).
  • Thurmond II, K. Bruce et al., “The Study of Shell Cross-Linked Knedels (SCK), Formation and Application”, ACS Polym. Prepr. (Div Polym. Chem.), Vol. 38, No. 1, pp. 62-63 (1997).
  • Thurmond, K. Bruce et al., “Shell cross-linked polymer micelles: stabilized assemblies with great versatility and potential”, Colloids and Surfaces B: Biointerfaces, vol. 16, pp. 45-54, 1999.
  • Tsitsilianis, Constantinos et al., Makromol. Chem. 191, pp. 2319-2328 (1990).
  • Tuzar, Zdenek et al., “Micelles of Block and Graft Copolymers in Solutions”, Surface and Colloid Science, vol. 15, Chapter 1, pp. 1-83 (1993).
  • Vamvakaki, M. et al., “Synthesis of novel block and statistical methacrylate-based ionomers containing acidic, basic or betaine residues”, Polymer, vol. 39, No. 11, pp. 2331-2337 (1998).
  • van der Maarel, J.R.C. et al., “Salt-Induced Contraction of Polyelectrolyte Diblock Copolymer Micelles”, Langmuir, vol. 16, No. 19, pp. 7510-7519 (2000).
  • Wang, Xiaorong et al., “Chain conformation in two-dimensional dense state”, Journal of Chemical Physics, vol. 121, No. 16, pp. 8158-8162 (Oct. 22, 2004).
  • Wang, Xiaorong et al., “Strain-induced nonlinearity of filled rubbers”, Physical Review E 72, 031406, pp. 1-9 (Sep. 20, 2005).
  • Pre-print article, Wang, Xiaorong et al., “PMSE 392- Manufacture and Commercial Uses of Polymeric Nanoparticles”, Division of Polymeric Materials: Science and Engineering (Mar. 2006).
  • Wang, Xiaorong et al., “Manufacture and Commercial Uses of Polymeric Nanoparticles”, Polymeric Materials: Science and Engineering, vol. 94, p. 659 (2006).
  • Wang, Xr. et al., “Fluctuations and critical phenomena of a filled elastomer under deformation”, Europhysics Letters, vol. 75, No. 4, pp. 590-596 (Aug. 15, 2006).
  • Webber, Stephen E. et al., “Solvents and Self-Organization of Polymers”, NATO ASI Series, Series E: Applied Sciences, vol. 327, pp. 1-509 (1996).
  • Wilson, D.J. et al., “Photochemical Stabilization of Block Copolymers Micelles”, Eur. Polym. J., vol. 24, No. 7, pp. 617-621, 1988.
  • Wooley, Karen L, “From Dendrimers to Knedel-like Structures”, Chem. Eur. J., 3, No. 9, pp. 1397-1399 (1997).
  • Wooley, Karen L, “Shell Crosslinked Polymer Assemblies: Nanoscale Constructs Inspired from Biological Systems”, Journal of Polymer Science: Part A: Polymer Chemistry, vol. 38, pp. 1397-1407 (2000).
  • Worsfold, D.J., “Anionic Copolymerization of Styrene with p-Divinylbenzene”, Macromolecules, vol. 3, No. 5, pp. 514-517 (Sep.-Oct. 1970).
  • Zheng, Lei et al., “Polystyrene Nanoparticles with Anionically Polymerized Polybutadiene Brushes”, Macromolecules, 37, pp. 9954-9962 (2004).
  • Zilliox, Jean-Georges et al., “Preparation de Macromolecules a Structure en Etoile, par Copolymerisation Anionique”, J. Polymer Sci.: Part C, No. 22, pp. 145-156 (1968).
  • Oct. 20, 2005 Office Action from U.S. Appl. No. 11/104,759, filed Apr. 13, 2005 (12 pp.).
  • Aug. 21, 2006 Final Office Action from U.S. Appl. No. 11/104,759, filed Apr. 13, 2005 (14 pp.).
  • Dec. 22, 2006 Advisory Action from U.S. Appl. No. 11/104,759, filed Apr. 13, 2005 (3 pp.).
  • May 16, 2007 Office Action from U.S. Appl. No. 11/104,759, filed Apr. 13, 2005 (9 pp.).
  • Oct. 30, 2007 Final Office Action from U.S. Appl. No. 11/104,759, filed Apr. 13, 2005 (11 pp.).
  • Bridgestone Americas 2006 Presentation (14 pp.).
  • Ishizu, Koji et al., “Core-Shell Type Polymer Microspheres Prepared by Domain Fixing of Block Copolymer Films”, Journal of Polymer Science: Part A: Polymer Chemistry, vol. 27, pp. 3721-3731 (1989).
  • Ishizu, Koji et al., “Preparation of core-shell type polymer microspheres from anionic block copolymers”, Polymer, vol. 34, No. 18, pp. 3929-3933 (1993).
  • O'Reilly, Rachel K. et al., “Functionalization of Micelles and Shell Cross-linked Nanoparticles Using Click Chemistry”, Chem. Mater., vol. 17, No. 24, pp. 5976-5988 [Nov. 24, 2005].
  • Saito, Reiko et al., “Core-Shell Type Polymer Microspheres Prepared From Poly(Styrene-b-Methacrylic Acid)—1. Synthesis of Microgel”, Eur. Polym. J., vol. 27, No. 10, pp. 1153-1159 (1991).
  • Saito, Reiko et al., “Arm-number effect of core-shell type polymer microsphere: 1. Control of arm-number of microsphere”, Polymer, vol. 35, No. 4, pp. 866-871 (1994).
  • Kralik, M. et al., “Catalysis by metal nanoparticles supported on functional organic polymers”, Journal of Molecular Catalysis A: Chemical, vol. 177, pp. 113-138 [2001].
  • Wang, Xiaorong et al., U.S. Appl. No. 10/791,049, filed Mar. 2, 2004 entitled “Method Of Making Nano-Particles Of Selected Size Distribution”.
  • Wang, Xiaorong et al., U.S. Appl. No. 10/791,177, filed Mar. 2, 2004 entitled “Rubber Composition Containing Functionalized Polymer Nanoparticles”.
  • Wang, Xiaorong et al., U.S. Appl. No. 10/872,731, filed Jun. 21, 2004 entitled “Reversible Polymer/Metal Nano-Composites And Method For Manufacturing Same”.
  • Wang, Xiaorong et al., U.S. Appl. No. 10/886,283, filed Jul. 6, 2004 entitled “Hydropobic Surfaces with Nanoparticles”.
  • Wang, Xiaorong et al., U.S. Appl. No. 11/058,156, filed Feb. 15, 2005 entitled “Multi-Layer Nano-Particle Preparation And Applications”.
  • Wang, Xiaorong et al., U.S. Appl. No. 11/104,759, filed Apr. 13, 2004 entitled “Nano-Particle Preparation And Applications”.
  • Bohm, Georg G.A. et al., U.S. Appl. No. 11/117,981, filed Apr. 29, 2005 entitled “Self Assembly Of Molecules To Form Nano-Particle”.
  • Wang, Xiaorong et al., U.S. Appl. No. 11/305,279, filed Dec. 16, 2005 entitled “Combined Use Of Liquid Polymer And Polymeric Nanoparticles For Rubber Applications”.
  • Wang, Xiaorong et al., U.S. Appl. No. 11/344,861, filed Feb. 1, 2006 entitled “Nano-Composite And Compositions Therefrom”.
  • Wang, Xiaorong et al., U.S. Appl. No. 11/642,796, filed Dec. 20, 2006 entitled “Hollow Nano-Particles And Method Thereof”.
  • Wang, Xiaorong et al., U.S. Appl. No. 11/764,607, filed Jun. 18, 2007 entitled “Multi-Layer Nano-Particle Preparation and Applications”.
  • Warren, Sandra, U.S. Appl. No. 11/771,659, filed Jun. 29, 2007 entitled “One-Pot Synthesis Of Nanoparticles And Liquid Polymer For Rubber Applications”.
  • Wang, Xiaorong et al., U.S. Appl. No. 11/941,128, filed Nov. 16, 2007 entitled “Nano-Particle Preparation And Applications”.
  • Wang, Xiaorong et al., U.S. Appl. No. 11/954,268, filed Dec. 12, 2007 entitled “Nanoporous Polymeric Material And Preparation Method”.
  • Wang, Xiaorong et al., U.S. Appl. No. 12/047,896, filed Mar. 13, 2008 entitled “Reversible Polymer/Metal Nano-Composites And Method For Manufacturing Same”.
  • Wang, Xiaorong et al., U.S. Appl. No. 12/184,895, filed Aug. 1, 2008 entitled “Disk-Like Nanoparticles”.
  • Harlan, Robert D., Final Office Action dated Dec. 10, 2008 from U.S. Appl. No. 10/791,177 (8 pp.).
  • Cain, Edward J., Final Office Action dated Dec. 9, 2008 from U.S. Appl. No. 11/642,795 (6 pp.).
  • Mulcahy, Peter D., Restriction/Election Office Action dated Dec. 11, 2008 from U.S. Appl. No. 11/642,802 (7 pp.).
  • Lipman, Bernard, Notice of Allowance dated Jan. 27, 2009 from U.S. Appl. No. 11/764,607 (4 pp.).
  • Johnson, Edward M., International Search Report dated Dec. 12, 2008 from PCT Application No. PCT/US07/74611 (5 pp.).
  • Wang, Xiaorong et al., U.S. Appl. No. 12/374,883 international filing date Jul. 27, 2007, entitled “Polymeric Core-Shell Nanoparticles with Interphase Region”.
  • Mullis, Jeffrey C., Mar. 11, 2009 Office Action from U.S. Appl. No. 10/791,049 (9 pp.).
  • Harlan, Robert D., Mar. 11, 2009 Notice of Allowance from U.S. Appl. No. 10/791,177 (8 pp.).
  • Sykes, Altrev C., Mar. 20, 2009 Office Action from U.S. Appl. No. 11/818,023 (27 pp.).
  • Pak, Hannah J., Apr. 2, 2009 Office Action from U.S. Appl. No. 11/941,128 (9 pp.).
  • Cui, Honggang et al., “Block Copolymer Assembly via Kinetic Control”, Science, vol. 317, pp. 647-650 (Aug. 3, 2007).
  • Wang, Xiaorong et al., “Under microscopes the poly(styrene/butadiene) nanoparticles”, Journal of Electron Microscopy, vol. 56, No. 6, pp. 209-216 (2007).
  • Wang, Xiaorong et al., “Heterogeneity of structural relaxation in a particle-suspension system”, EPL, 79, 18001, pp. 1-5 (Jul. 2007).
  • Borukhov, Itamar et al., “Enthalpic Stabilization of Brush-Coated Particles in a Polymer Melt”, Macromolecules, vol. 35, pp. 5171-5182 (2002).
  • Braun, Hartmut et al., “Enthalpic interaction of diblock copolymers with immiscible polymer blend components”, Polymer Bulletin, vol. 32, pp. 241-248 (1994).
  • Brown, H.R. et al., “Communications to the Editor: Enthalpy-Driven Swelling of a Polymer Brush”, Macromolecules, vol. 23, pp. 3383-3385 (1990).
  • Cahn, John W., “Phase Separation by Spinodal Decomposition in Isotropic Systems”, The Journal of Chemical Physics, vol. 42, No. 1, pp. 93-99 (Jan. 1, 1965).
  • Chen, Ming-Qing et al., “Nanosphere Formation in Copolymerization of Methyl Methacrylate with Poly(ethylene glycol) Macromonomers”, Journal of Polymer Science: Part A: Polymer Chemistry, vol. 38, pp. 1811-1817 (2000).
  • Ferreira, Paula G. et al., “Scaling Law for Entropic Effects at Interfaces between Grafted Layers and Polymer Melts”, Macromolecules, vol. 31, pp. 3994-4003 (1998).
  • Gay, C., “Wetting of a Polymer Brush by a Chemically Identical Polymer Melt”, Macromolecules, vol. 30, pp. 5939-5943 (1997).
  • Halperin, A., “Polymeric Micelles: A Star Model”, Macromolecules, vol. 20, pp. 2943-2946 (1987).
  • Hasegawa, Ryuichi et al., “Optimum Graft Density for Dispersing Particles in Polymer Melts”, Macromolecules, vol. 29, pp. 6656-6662 (1996).
  • Kraus, Gerard, “Mechanical Losses in Carbon-Black-Filled Rubbers”, Journal of Applied Polymer Science: Applied Polymer Symposium, vol. 39, pp. 75-92 (1984).
  • Ligoure, Christian, “Adhesion between a Polymer Brush and an Elastomer: A Self-Consistent Mean Field Model”, Macromolecules, vol. 29, pp. 5459-5468 (1996).
  • Ma, H. et al., Reverse Atom Transfer Radical Polymerization of Methyl Methacrylate in Room-Temperature Ionic Liquids, J. Polym. Sci., A Polym. Chem., 41, pp. 143-151 (2003).
  • Matsen, M.W., “Phase Behavior of Block Copolymer/Homopolymer Blends”, Macromolecules, vol. 28, pp. 5765-5773 (1995).
  • Milner, S.T. et al., “Theory of the Grafted Polymer Brush”, Macromolecules, vol. 21, pp. 2610-2619 (1988).
  • Milner, S.T. et al., “End-Confined Polymers: Corrections to the Newtonian Limit”, Macromolecules, vol. 22, pp. 489-490 (1989).
  • Noolandi, Jaan et al., “Theory of Block Copolymer Micelles in Solution”, Macromolecules, vol. 16, pp. 1443-1448 (1983).
  • Semenov, A.N., “Theory of Diblock-Copolymer Segregation to the Interface and Free Surface of a Homopolymer Layer”, Macromolecules, vol. 25, pp. 4967-4977 (1992).
  • Semenov, A.N., “Phase Equilibria in Block Copolymer-Homopolymer Mixtures”, Macromolecules, vol. 26, pp. 2273-2281 (1993).
  • Shull, Kenneth R., “End-Adsorbed Polymer Brushes in High- and Low-Molecular-Weight Matrices”, Macromolecules, vol. 29, pp. 2659-2666 (1996).
  • Whitmore, Mark Douglas et al., “Theory of Micelle Formation in Block Copolymer-Homopolymer Blends”, Macromolecules, vol. 18, pp. 657-665 (1985).
  • Wijmans, C.M. et al., “Effect of Free Polymer on the Structure of a Polymer Brush and Interaction between Two Polymer Brushes”, Macromolecules, vol. 27, pp. 3238-3248 (1994).
  • Witten, T.A. et al., “Stress Relaxation in the Lamellar Copolymer Mesophase”, Macromolecules, vol. 23, pp. 824-829 (1990).
  • Worsfold, Denis J. et al., “Preparation et caracterisation de polymeres-modele a structure en etoile, par copolymerisation sequencee anionique”, Canadian Journal of Chemistry, vol. 47, pp. 3379-3385 (Mar. 20, 1969).
  • Haider, Saira Bano, Mar. 3, 2009 Advisory Action from U.S. Appl. No. 11/104,759 (3 pp.).
  • Lipman, Bernard, Notice of Allowance dated Jan. 14, 2009 from U.S. Appl. No. 11/058,156 (5 pp.).
  • Harlan, Robert D., Offie Action dated Jan. 9, 2009 from U.S. Appl. No. 11/117,981 (6 pp.).
  • Cain, Edward J., Notice of Allowance dated Dec. 31, 2008 from U.S. Appl. No. 11/642,124 (5 pp.).
Patent History
Patent number: 7597959
Type: Grant
Filed: Dec 19, 2006
Date of Patent: Oct 6, 2009
Patent Publication Number: 20080145660
Assignee: Bridgestone Corporation
Inventors: Xiaorong Wang (Hudson, OH), Christine Rademacher (Akron, OH)
Primary Examiner: H. (Holly) T Le
Attorney: Meredith E. Hooker
Application Number: 11/612,554